Chemically reversible four-electron oxidation and reduction utilizing two inorganic functional groups

Michael Nippe; Samuel M Goodman; Charles G Fry; John F Berry

doi:10.1021/ja1114248

Chemically reversible four-electron oxidation and reduction utilizing two inorganic functional groups

J Am Chem Soc. 2011 Mar 9;133(9):2856-9. doi: 10.1021/ja1114248. Epub 2011 Feb 14.

Authors

Michael Nippe¹, Samuel M Goodman, Charles G Fry, John F Berry

Affiliation

¹ Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.

PMID: 21319824
DOI: 10.1021/ja1114248

Abstract

Four-electron oxidation of the quadruply bonded W(2)(II,II) compound W(2)(2,2'-dipyridylamide)(4), 1, results in the formation of a novel, diamagnetic ditungsten terminal oxo compound [W(2)O(2,2'-dipyridylamide)(4)](2+), 2. In contrast to the chemical inertness of mononuclear tungsten oxo species, 2 undergoes a four-electron reduction including oxygen-atom transfer in reactions with excess tri-tert-butylphosphine in acetonitrile to recover 1. This unusual chemically reversible multielectron reactivity is ascribed to the cooperation of W-O and W-W multiple bonding.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

2,2'-Dipyridyl / analogs & derivatives*
Amides / chemistry
Crystallography, X-Ray
Models, Molecular
Oxidation-Reduction
Tungsten Compounds / chemistry*

Substances

Amides
Tungsten Compounds
2,2'-Dipyridyl